Method of foaming thermoplastic polycarbonate

ABSTRACT

A method of foaming thermoplastic aromatic polycarbonates is disclosed. Accordingly, a polycarbonate resin is mixed with 0.01 to 10%, the percent being relative to the total weight of polycarbonate resin and polysaccharide, of a particular polysaccharide and the mixture then processed thermoplastically without the application of negative pressure in an extruder, at temperatures of 180° C. to 320° C., or in an injection molding machine, at temperatures of 190° C. to 330° C., to obtain foamed molded articles.

This application is a division of application Ser. No. 7/989,391 filedDec. 11, 1992, U.S. Pat. No. 5,223,548.

FIELD OF THE INVENTION

The invention relates to foamable thermoplastic molding compositions andmore particularly to polycarbonate based compositions containingpolysaccharides.

SUMMARY OF THE INVENTION

A method of foaming thermoplastic aromatic polycarbonates is disclosed.Accordingly, a polycarbonate resin is mixed with 0.01 to 10%, thepercent being relative to the total weight of polycarbonate resin andpolysaccharide, of a particular polysaccharide and the mixture thenprocessed thermoplastically without the application of negative pressurein an extruder, at temperatures of 180° C. to 320° C., or in aninjection molding machine, at temperatures of 190° C. to 330° C., toobtain foamed molded articles.

BACKGROUND OF THE INVENTION

High-molecular polycarbonate foamed plastics are known (see e.g. DE-AS1,031,507). The foaming agents can be e.g. substances which split offCO₂ or inert gases such as N₂ or CO₂.

Polycarbonates are severely degraded in the presence of amides (see e.g.H. Schnell, Chemistry and Physics of Polycarbonates, IntersciencePublishers, New York 1964, page 183).

The use of natural substances for foaming polycarbonates is not taughtin the technical literature.

DETAILED DESCRIPTION OF THE INVENTION

The invention relates to a method of foaming thermoplastic aromaticpolycarbonates characterized in that thermoplastic aromaticpolycarbonates are mixed with 0.01 to 10, preferably 0.05 to 4 andparticularly 0.1 to 2% by weight, relative to the total weight ofpolycarbonate polysaccharide, of amide group-containing polysaccharidesand are either extruded at temperatures of 180° C. to 320° C. inextruders without application of negative pressure, to obtain foamedmolded members, or are injection molded at temperatures of 190° C. to330° C. in injection-molding machines to obtain foamed molded members.

Completely unexpectedly, it has been found that polycarbonate can befoamed by adding amide-containing polysaccharides without significantlyreducing the molecular weight of the thermoplastic polycarbonate.

The polycarbonate foam obtainable by the method according to theinvention is not discolored and has high tenacity, low density and agood cell structure.

The invention therefore also relates to use of amide group-containingpolysaccharides for foaming thermoplastic aromatic polycarbonates.

The invention also relates to the polycarbonate foamed molded membersobtainable by the method according to the invention.

The polysaccharides according to the invention are amide or aminegroup-containing polysaccharides or oligosaccharides. These may beobtained from natural raw materials or by synthetic means.

Preferably the polysaccharides are chitin or chitin derivatives such aschitosan, particularly preferably chitin. Chitin in the sense accordingto the invention is a (1→4)-β-Polymer of 2-acetamido-2-deoxy-D-glucosehaving the following structure: ##STR1##

The chitin used according to the invention has a residual moisturecontent of 2-15, preferably 5-11% by weight of water. The water contentof the chitin and the polycarbonate together is not sufficient forfoaming, and consequently water is not the preferred foaming agent. Thenitrogen content of chitin according to the invention is between 6.0 and7.0% by weight, and the degree of acetylation is between 85 and 100%.The ash content (900° C.) is 0.1-1.3% by weight. Chitin according to theinvention has a molecular weight of 10,000-1,000,000, preferably100,000-600,000.

In nature, chitin mainly occurs as a component of the cell walls or theouter skeleton of fungi, algae, protozoa, cnidaria, aschelmintes,endoprocta, bryozoa, phoronidea, brachiopoda, echiurida, annelida,mollusca, pogonophora and particularly anthropoda (crustacea, insecta,arachnida and chilopoda). With regard to the occurrence and biosynthesisof chitin, see R. A. Muzarelli, Chitin, Pergamon Press, Oxford, 1977,pages 5 ff. All chitin modifications and mixtures thereof, particularlymaterial obtained from crustaceae, are suitable for foaming according tothe invention.

Chitin flakes with edge lengths up to 2 cm and a thickness up to 1 mm,or preferably finely-ground material are suitable for foamingpolycarbonate according to the invention. The foaming agent is added inconventional metering devices, in solution or preferably solid form oras a concentrated granulate in polycarbonate or in other plasticsmiscible with polycarbonate.

Impure chitin, e.g. from waste from the fish or crab or similarindustry, can also be used for foaming according to the invention. Thechitin content of the waste can be from 40 to 100% by weight of the drymaterial, preferably 70-100% by weight of the dry material, theremainder being native residues of the animals or plants used as thesource of chitin.

Exhaustive information about chitin and chitin products can be found inR. A. Muzarelli, Chitin, Pergamon Press, Oxford, 1977; G. O. Aspinall,The Polysaccharides, Vol. 3, Academic Press, Orlando, 1985; W. A. Wood,S. T. Kellog, Methods in Enzymology, vol. 161; Biomass, Part B (Lignin,Pectin, and Chitin), Academic Press, San Diego, 1988; G. Skjak-Braek, T.Anthonson, P. Sandford (Ed.), Chitin and Chitosan, Elsevier, London/NewYork, 1989.

Chitosan according to the invention is partly or completely deacetylatedchitin with an acetylation coefficient of 0-85%, preferably 30-60%. Forfurther details, see the previously-cited literature.

Chitin derivatives according to the invention contain e.g. N-acylchitosans, N-carboxyalkyl (aryl) chitosans, O-carboxyl alkyl chitosansand chitins, derivatives resulting from incorporation or exchange ofsugar units, metal ion chelates, graft copolymers on chitin or chitosanand other chemical modifications of chitin or chitosans.

The impure chitin, chitosan or chitin derivatives according to theinvention can be added in metered manner as described in the case ofchitin.

The thermoplastic aromatic polycarbonates according to the invention arepolycarbonates prepared from diphenols and carbonate donors by theconventional methods known from the literature (see e.g. H. Schnell,Chemistry and Physics of Polycarbonates, Interscience Publishers, NewYork, 1964, U.S. Pat. No. 3,028,365 and German Offenlegungsschrift3,832,396 (LeA 26,344)).

The diphenols for these polycarbonates can be e.g. hydroquinone,resorcinol, dihydroxydiphenol, bis-(hydroxyphenyl) alkanes,bis-(hydroxyphenyl) cycloalkanes, bis-(hydroxyphenyl) sulphides,bis-(hydroxyphenyl) ethers, bis-(hydroxy phenyl) ketones,bis-(hydroxyphenyl) sulphones, bis-(hydroxyphenyl) sulphoxides,α,α'-bis-(hydroxyphenyl) diisopropyl benzenes or alkylated-ring orhalogenated-ring compounds thereof.

The following are examples of preferred diphenols:4,4'-dihydroxydiphenyl, 2,2-bis-(4-hydroxyphenyl) propane,2,4-bis-(4-hydroxyphenyl)-2-methyl butane,1,1-bis-(4-hydroxyphenyl)-p-diisopropanol benzene,2,2-bis-(3-methyl-4-hydroxyphenyl) propane,2,2-bis-(3-chloro-4-hydroxyphenyl) propane,bis-(3,5-dimethyl-4-hydroxymethyl) methane,2,2-bis-(3,5-dimethyl-4-hydroxyphenyl) propane,bis-(3,5-dimethyl-4-hydroxyphenyl) sulphone,2,4-bis-(3,5-dimethyl-4-hydroxyphenyl)-2-methyl butane,1,1-bis-(3,5-dimethyl-4-hydroxyphenyl)-p-diisopropyl benzene,2,2-bis-(3,5-dichloro-4-hydroxyphenyl) propane,2,2-bis-(3,5-dibromo-4-hydroxyphenyl) propane or1,1-bis(4-hydroxyphenyl)-3,3,5-trimethyl cyclohexane.

The following are examples of particularly preferred diphenols:2,2-bis-(4-hydroxyphenyl) propane,2,2-bis-(3,5-dimethyl-4-hydroxyphenyl) propane,2,2-bis-(3,S-dichloro-4-hydroxyphenyl)-propane,2,2bis(3,5-dibromo-4-hydroxyphenyl) propane, 1,1-bis-(4-hydroxyphenyl)cyclohexane or 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethyl cyclohexane,(2-hydroxyphenyl)-(4-hydroxyphenyl) methane, bis-(4-hydroxyphenyl)methane, bis-C₄ - hydroxyphenyl) sulphide or bis-(4-hydroxyphenyl)sulphone.

The diphenols can be used either alone or mixed with one another, i.e.both homopolycarbonates and copolycarbonates are included. Djphenols areknown from the literature or can be produced by methods known from theliterature.

Use also can be made of small quantities, preferably quantities between0.05 and 2.0 mol relative to the mols of diphenols used, of tri- or morethan trifunctional compounds, more particularly compounds with three ormore than three phenolic hydroxyl groups. The following are examples ofsome useable compounds with three or more than three phenolic hydroxylgroups:

Phloroglucinol, 4,6-dimethyl-2,4,6-tri-4-(4-hydroxyphenyl) heptene2,4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl) heptane,1,3,5-tri-(4-hydroxyphenyl) benzene, 1,1,1-tri-(4-hydroxyphenyl) ethane,Tri-(4-hydroxyphenyl) phenyl methane, 2,2-bis-[4,4-bis-(4-hydroxyphenyl)cyclohexyl]propane, 2,4-bis-(4-hydroxyphenyl-isopropyl) phenol,2,6-bis-(2- hydroxy-5'-methylbenzyl)-4-methyl phenol,2-(4-hydroxyphenyl)-2-(3,4-dihydroxyphenyl) propane,Hexa-(4-(4-hydroxyphenylisopropyl)-phenyl) orthoterephthalic acid ester,tetra-(4-hydroxyphenyl) methane,Tetra-(4-(4-hydroxyphenyl-isopropyl)-phenoxy) methane and1,4-bis-(4',4"-dihydroxytriphenyl) methyl benzene.

2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and3,3-bis-(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole are otherpossible branching agents.

The optionally additionally-used 0.05 to 2 mol relative to diphenols, ofbranching agents can be supplied either with the diphenols themselvesand the molecular-weight regulators in the aqueous alkaline phase or canbe dissolved in an organic solvent and added before phosgenization.

The molecular-weight regulators can be the known substances, preferablymonophenols.

The aromatic polycarbonates according to the invention should haveweight average molecular weights Mw (obtained by gel permeationchromatography) between 5,000 and 50,000, preferably between 15,000 and35,000.

The corresponding viscosities in solution are between 1.15 and 1.35,measured in dichloromethane (0.5 g/100 ml).

Thermoplastic aromatic polycarbonates in the sense of the inventioninclude thermoplastic aromatic polyester carbonates, i.e."polycarbonates" in which a part, up to 50 mol of carbonate structuralunits are replaced by aromatic dicarboxylate structural units in knownmanner.

The following are examples of suitable aromatic dicarboxylic acids:orthophthalic acid, terephthalic acid, isophthalic acid, tert. butylisophthalic acid, 3,3'-diphenyl dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid,4,4'-benzophenone dicarboxylic acid, 3,4'-benzophenone dicarboxylicacid, 4,4'-diphenyl sulphone dicarboxylic acid,2,2-bis-(4-carboxyphenyl) propane or trimethyl-3-phenylindane-4,5-dicarboxylic acid.

Among aromatic dicarboxylic acids, terephthalic acid and/or isophthalicacid are particularly preferred.

The diphenols previously mentioned for manufacture of polycarbonate aresuitable.

The same applies to the branching agents and the monophenolicchain-breaking agents, but in this case use can also be made of aromaticmonocarboxylic acids, e.g. in the form of their acid chlorides oresters.

Carbon dioxide can be incorporated in the polyester carbonates eithervia COCl₂ or via diphenyl carbonate, depending on the chosen method ofmanufacture, i.e. manufacture of polyester carbonate by interphasepolycondensation or melt transesterification.

The same applies to the aromatic dicarboxylic acids; they are used inthe form either of aromatic dicarboxylic acid dichlorides in thetwo-phase interface process or in the form of dicarboxylic acid diestersin the melt transesterification process. The same applies ifmonocarboxylic acids are used as chain-breaking agents.

The polyester carbonates for foaming according to the invention areprepared by conventional methods, e.g. by the interphase method or themelt transesterification method as already mentioned.

The polyester carbonates for foaming can therefore be eitherstraight-chain or branched in known manner.

The aromatic polyester carbonates according to the invention have weightaverage molecular weights Mw (determined by gel permeationchromatography) between 5,000 and 50,000, preferably between 15,000 and35,000.

The corresponding viscosities in solution are between 1.15 and 1.35,measured in dichloromethane (0.5 g/100 ml).

The molar ratio of carbonate units to aromatic dicarboxylate units inthe polyester carbonates for foaming according to the invention is atleast about 50:50, preferably about 75:25 and particularly about 90:10.

The polycarbonates used in the foaming process according to theinvention are either dried or non-dried, preferably non-dried, i.e. thepolycarbonates preferably have an H₂ O content of 0.01 to 0.1% byweight.

In the method of foaming according to the invention, use can also bemade of conventional foaming additives such as reinforcing substances,e.g. glass fibers, and/or nucleating agents and/or flame-retardantsand/or mold-release agents and/or dyes and/or pigments, e.g. rutile orcarbon black and/or stabilizers against heat, UV radiation and moisture.

The following are examples of suitable flame-retardants, used inproportions of up to 10% by weight relative to the content ofpolycarbonate: tetrachlorophthalic acid anhydride, tetrabromophthalicacid anhydride, tetrachlorobisphenol-A (monomer or oligomer),tetrabromobisphenol-A (monomer or oligomer) or perfluorobutane sulphonicacid Na or K salt, alone or mixed with poly(tetrafluoroethylene) powder.

The invention therefore also relates to foaming of thermoplasticaromatic polycarbonates with a content of conventional additives,characterized in that themoplastic aromatic polycarbonates, afteraddition of the conventional additives, are mixed with 0.01 to 10,preferably 0.05 to 4, particularly 0.1 to 2% by weight, relative to thetotal weight of polycarbonate+polysaccharide, of amide-containingpolysaccharides and without application of negative pressure is eitherextruded at temperatures of 180° C. to 320° C. in an extruder to obtainfoamed molded members or injection-molded at temperatures of 190° C. to330° C. in injection molding machines to obtain foamed molded members.

The invention also relates to the additive-containing polycarbonatefoamed molded members obtainable by the aforementioned method accordingto the invention.

The method according to the invention can also be extended by mixingother thermoplastics with the polycarbonates to be foamed, theproportion of polycarbonates for foaming according to the inventionmaking up 10 to 100, preferably 20 to 100 and particularly 50 to 100% byweight, relative to the weight of the mixture of polycarbonate and otherthermoplastics.

The other thermoplastics are preferably thermoplastic polyesters,preferably thermoplastic polyalkylene terephthalates, or ASS polymers,SAN polymers, polysulphones or polyamides, preferably microcrystalline("amorphous") polyamides, or polyolefins.

The foaming process is not adversely effected by the presence of theseother thermoplastics.

The invention therefore also relates to foaming of thermoplasticaromatic polycarbonates mixed with up to 90, preferably up to 80 andparticularly up to 50% by weight of other thermoplastics, relative tothe total mixture of polycarbonate and other thermoplastics,characterized in that the thermoplastic aromatic polycarbonates arefoamed according to the invention when mixed with the respectiveproportions by weight of other thermoplastics.

The previously-mentioned conventional additives can be used in this casealso.

The invention also relates to polycarbonate foam obtainable by theaforementioned method according to the invention and containing otherthermoplastics and optionally containing conventional additives.

Known impact-strength modifiers such as hydrogenated butadiene styrenecopolymers or acrylate graft rubber can also be added in conventionalproportions, e.g. up to 10% by weight relative to the weight ofpolycarbonate, to the polycarbonates for foaming according to theinvention.

The invention therefore also relates to foaming of thermoplasticaromatic polycarbonates in all the variants previously disclosed,characterized in that before the actual foaming operation,impact-strength modifiers are added to the polycarbonates in proportionsup to 10% by weight of the polycarbonate.

The invention also relates to polycarbonate foam molded membersobtainable by the aforementioned method.

The thermoplastic polyalkylene terephthalates also used according to theinvention are e.g. based on ethylene glycol, propane -1,3-diol, butane-1,4-diol, hexane -1,6-diol or 1,4-bis- hydroxymethyl cyclohexane. Themolecular weight (Mw) of these polyalkylene glycol terephthalates isbetween 10,000 and 80,000. The polyalkylene glycol terephthalates can beobtained by known methods, e.g. from terephthalate acid dialkyl esterand the corresponding diol by transesterification. For example, thestarting product is a low alkyl ester of terephthalic acid, preferablythe dimethyl ester, which is esterified with an excess of diol in thepresence of suitable catalysts to obtain the bishydroxyalkyl ester ofterephthalic acid. In the process the temperature is increased from aninitial 140° C. to 210°-220° C. The liberated alcohol is distilled off.Condensation is then brought about at temperatures of 210°-280° C., thepressure being gradually lowered to below 1 Torr and the excess diolbeing distilled off.

The thermoplastic ABS polymers also used according to the invention aresubstances in which either a monomer from the series styrene, methylmethacrylate or a monomer mixture of 95-50% by weight of styrene,α-methyl styrene, methyl methacrylate or mixtures thereof and 5-50% byweight of acryl nitrile, methyl methacrylate, maleic acid anhydride,N-substituted maleic imides or mixtures thereof are graft-polymerized ona rubber. The rubber may more particularly be polybutadiene,butadiene/styrene copolymers with up to 30% by weight of styreneincorporated by polymerization, copolymers of butadiene andacrylonitrile with up to 20% by weight of acrylonitrile or copolymers ofbutadiene with up to 20% by weight of a low alkyl ether of acrylic ormethacrylic acid (e.g. methyl acrylate, ethyl acrylate, methylmethacrylate or ethyl methacrylate).

The graft copolymers contain 5-80, more particularly 20-70% by weight ofrubber and 95-20, more particularly 80-30% by weight ofgraft-copolymerized monomers. In these graft copolymers, the rubber isin the form of at least partially cross-linked particles having anaverage size of 0.09 to 5 μm, more particularly 0.1 to 1 μm. These graftcopolymers are obtained by radical graft copolymerization of monomersfrom the series styrene, α-methyl styrene, acrylonitrile, methylmethacrylate and maleic acid anhydride in the presence of the rubber tobe grafted and are well-known. The preferred methods of manufacturingthese graft copolymers are emulsion, solution, mass or suspensionpolymerization.

The thermoplastic SAN polymers also used according to the invention arecopolymers of 95-50 parts by weight of styrene, α-methyl styrene, methylmethacrylate or mixtures thereof and 5-50 parts by weight ofacrylonitrile, methacrylonitrile, methyl methacrylate or mixturesthereof. Among these copolymers, particular preference is given toproducts obtained from about 80-60% by weight of styrene and 20-40% byweight of acrylonitrile, and the corresponding copolymers of α-methylstyrene.

The polysulphones also used according to the invention are e.g.polycondensates containing inter alia sulphone units in the main chainwith a molecular weight between 1,000 and 200,000 (measured by gelchromatography) and prepared by conventional methods (see e.g. K. Idelin: Houben-Weyl, Methoden der Organischen Chemie, Volume E20, Part 2,pages 1467 ff., Thieme Verlag, Stuttgart 1987).

The polyamides also used according to the invention are polymers withrepeating carboxylic acid amide groups in the main chain, e.g.polycondensates of diamines with dicarboxylic acids or polycondensatesof lactams having a molecular weight (measured by gel chromatography) of1,000 to 100,000 and prepared by the conventional methods (see e.g. P.Matthies, R. V. Meyer in: Houben-Weyl, Methoden der Organischen Chemie,Volume E20, Part 2, pages 1497 ff, Thieme Verlag, Stuttgart 1987),materials with low crystallinity being preferred.

The thermoplastic polyolefins also used according to the invention arepolymers of aliphatic unsaturated hydrocarbons, e.g. ethylene,propylene, butylene or isobutylene obtained by conventional methods,e.g. radical polymerization, and having a weight average or molecularweight Mw (measured by gel chromatography) between 1,000 and 3,000,000.High-pressure polyolefin and low-pressure polyolefin can both be used.The unsaturated hydrocarbons can also be copolymerized with other vinylmonomers, e.g. vinyl acetate, in known manner.

The individual components, i.e. polycarbonates, amide group containingpolysaccharides, conventional additives, other thermoplastics and/orimpact strength modifiers can be previously mixed in known manner atvarious temperatures, preferably at room temperature.

The components can be mixed e.g. in solution, in methylene chloride orpreferably in the substance, the polysaccharides being finely groundwhen used.

Also, foaming agents in high concentrations (e.g. 3 to 7% by weight ofpolysaccharides according to the invention) can be incorporated andgranulated in polycarbonate or a thermoplastic polymer miscible withpolycarbonate and the mixture can be added in concentrated form, usingconventional metering devices, to the polycarbonates for foamingaccording to the invention.

The foaming process according to the invention is then carried out onconventional machines, e.g. single-screw extruders. The suitable methodsare free foaming, with or without cooled calibration, or inward foaming,i.e. the Celuka method.

The foamed plastics obtainable according to the invention can be moldedas required or cut to size after foaming. The molded members can e.g. betubes, plates and section members of widely varying kind, optionallydyed, coated or varnished. After foaming, they can be cut to size ormechanically or thermally shaped or processed by other means.

The foamed molded members obtained according to the invention canadvantageously be used for producing large-area covers over lamps,casings or office equipment or for producing large-area components suchas parts of cupboards or section members such as window-frames orstructural parts in the motor-vehicle or building sector.

EXAMPLES EXAMPLE 1

A mixture of 99% by weight of homopolycarbonate was extruded from2,2-bis-(4-hydroxyphenyl) propane (ηrel=1.283; 0.5% in methylenechloride) and 1% by weight of chitin. Extrusion was carried out on asingle-screw extruder. The temperature was 240° C. Foaming was carriedout without calibration, by the method of free foaming. The result was afine-pore closed cell foam having a density of 0.6 g/cm³. The relativeviscosity of the foam was ηrel=1.288 (0.5% in methylene chloride).

EXAMPLE 2

A mixture of 98% by weight of homopolycarbonate was extruded from2,2-bis-(4-hydroxyphenyl) propane (θrel=1.282; 0.5% in methylenechloride) and 2% by weight of chitin. Extrusion was carried out on asingle-screw extruder. The temperature was 230° C. Foaming was carriedout without calibration, by the method of free foaming. The result was afine-pore closed cell foam having a density of 0.75 g/cm³. The relativeviscosity of the foam was ηrel=1.284 (0.5% in methylene chloride).

EXAMPLE 3

A mixture of 99.5% by weight of homopolycarbonate was extruded from2,2-bis-(4-hydroxyphenyl) propane (ηrel=1.282; 0.5% in methylenechloride) and 0.5% by weight of chitin. Extrusion was carried out on asingle-screw extruder. The temperature was 260° C. Foaming was carriedout without calibration, by the method of free foaming. The result was afine-pore closed-cell foam having a density of 0.76 g/cm³. The relativeviscosity of the foam was ηrel=1.276 (0.5% in methylene chloride).

EXAMPLE 4

A mixture of 99% by weight of impact strength-modified glassfiber-reinforced homopolycarbonate from 2,2-bis-(4-hydroxyphenyl)propane (ηrel=1.28; 0.5% in methylene chloride) and 1% by weight ofchitin was processed at 310° C. on a double screw injection-moldingmachine. The resulting injection molded foam members were adjusted to adensity of 0.9 kg/l. The injection-molded foamed members efficientlyfilled the mold with a fine-pored uniform foam structure, which had arelative viscosity of ηrel=1.25 and was given the fire classificationVO.

We claim:
 1. A foamable thermoplastic molding composition comprising athermoplastic aromatic polycarbonate resin and about 0.01 to 10% of asaccharide compound, said percent being relative to the total weight ofpolycarbonate resin and saccharide compound, said saccharide being atleast one member selected from the group consisting of aminegroup-containing polysaccharide, amide group-containing polysaccharide,amine group-containing oligo-saccharide, and amide group-containingoligo-saccharide.
 2. The composition of claim 1 wherein said saccharideis chitin.
 3. The composition of claim 1 wherein said percent is about0.5 to 4 percent.
 4. A foamed molded article obtained by a methodcomprising(i) mixing a thermoplastic aromatic polycarbonate resin andabout 0.01 to 10% of a saccharide compound to form a mixture, saidpercent being relative to the total weight of polycarbonate resin andsaccharide compound, said saccharide being at least one member selectedfrom the group consisting of amine group-containing polysaccharide,amide group-containing polysaccharide, amine group-containingoligo-saccharide, and amide group-containing oligo-saccharide, and (ii)processing said mixture without application of negative pressure in anextruder at temperatures of 180° C. to 320° C., or in an injectionmolding machine at temperatures of 190° C. to 330° C.
 5. The article ofclaim 4 wherein said mixture further comprises up to 10% of an impactmodifier, said percent being relative to the weight of saidpolycarbonate.